WO2016021577A1 - 特殊形状を有するエポキシ樹脂成形物、及びそれを備えた光学装置 - Google Patents
特殊形状を有するエポキシ樹脂成形物、及びそれを備えた光学装置 Download PDFInfo
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- WO2016021577A1 WO2016021577A1 PCT/JP2015/072041 JP2015072041W WO2016021577A1 WO 2016021577 A1 WO2016021577 A1 WO 2016021577A1 JP 2015072041 W JP2015072041 W JP 2015072041W WO 2016021577 A1 WO2016021577 A1 WO 2016021577A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00269—Fresnel lenses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
- B29C39/006—Monomers or prepolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/026—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles characterised by the shape of the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
- B29D11/00442—Curing the lens material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/105—Onium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0012—Arrays characterised by the manufacturing method
- G02B3/0031—Replication or moulding, e.g. hot embossing, UV-casting, injection moulding
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/02—Simple or compound lenses with non-spherical faces
- G02B3/08—Simple or compound lenses with non-spherical faces with discontinuous faces, e.g. Fresnel lens
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0082—Flexural strength; Flexion stiffness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
- B29L2011/0016—Lenses
Definitions
- the present invention relates to an epoxy resin molded product having a large thickness deviation ratio and an optical device including the same.
- This application includes Japanese Patent Application No. 2014-162669 filed in Japan on August 8, 2014, Japanese Patent Application No. 2014-221124 filed in Japan on October 30, 2014, and Japanese Patent Application on March 18, 2015. Claims the priority of Japanese Patent Application No. 2015-054459, which is incorporated herein by reference.
- thermoplastic resin such as polycarbonate, polymethyl methacrylate (PMMA), cycloolefin polymer (COP) or the like
- PMMA polymethyl methacrylate
- COP cycloolefin polymer
- Patent Documents 1 and 2 a method of injection molding using a thermoplastic resin such as polycarbonate, polymethyl methacrylate (PMMA), cycloolefin polymer (COP) or the like.
- the thermoplastic resin has low fluidity, when producing a molded product with a large uneven thickness ratio, injection molding may cause unfilled parts in the thin part, or the filling speed to the thin part compared to the thick part. It has been a problem that the appearance defect and the mechanical strength decrease due to the occurrence of a weld line due to the slowing of the deformation.
- an object of the present invention is to provide a molded article having a shape exhibiting a light condensing or light diffusing effect, which is excellent in mechanical strength and heat resistance and has a high thickness deviation ratio.
- Another object of the present invention is to provide a molded article having a shape that exhibits a light condensing or light diffusing effect, which is excellent in mechanical strength and heat resistance, and has a high deviation ratio and a thin portion. is there.
- Another object of the present invention is a molded product having a shape that exhibits a light condensing or light diffusing effect, and is excellent in transferability, mechanical strength, and heat resistance of a mold (mold), and has a high deviation ratio and a thin wall.
- the object is to provide a molded product having a part.
- Another object of the present invention is to provide a method for producing the molded product.
- Another object of the present invention is to provide an optical device provided with the molded article.
- the inventors of the present invention are molded products having a shape that exhibits a light condensing or light diffusing effect by subjecting the curable composition containing the epoxy compound (A) to casting molding.
- the curable composition containing the epoxy compound (A) is molded products having excellent mold transferability, mechanical strength, and heat resistance and a large uneven thickness ratio.
- the present invention has been completed based on these findings.
- this invention is a hardened
- the present invention also provides the above molded product, wherein the thickness of the thinnest part of the molded product is 0.2 mm or less.
- the present invention also provides the molded article, wherein the epoxy compound (A) contains a compound represented by the following formula (a).
- R 1 to R 18 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.
- X represents a single bond or a linking group
- the present invention also provides the molded article, wherein the epoxy compound (A) is a compound represented by the formula (a) and contains a compound not containing an ester bond.
- the present invention also provides the molded article, wherein the curable composition contains an epoxy compound (A), an oxetane compound (B), and a cationic polymerization initiator (C).
- the curable composition contains an epoxy compound (A), an oxetane compound (B), and a cationic polymerization initiator (C).
- the present invention also provides the molded article, wherein the cationic polymerization initiator (C) is a photocationic polymerization initiator.
- the present invention also provides the above molded article, wherein the curable composition further contains an antioxidant (D).
- the present invention also provides the above-mentioned molded product, wherein the molded product having a light collecting or light diffusion effect is a Fresnel lens.
- the present invention also provides a method for producing a molded product, which is obtained by subjecting the curable composition containing the epoxy compound (A) to casting molding.
- the present invention also provides a method for producing the molded article, which has the following steps.
- Step 1 Step of filling a transparent array mold with a photocurable composition containing an epoxy compound (A)
- Step 2 Step of irradiating the photocurable composition with light to obtain a molded product array
- Step 3 Molded product array The process of separating
- the present invention also provides a method for producing the above molded article, in which light irradiation is performed using a UV-LED (wavelength: 350 to 450 nm).
- the present invention also provides a method for producing the molded product, wherein the cumulative amount of light irradiation is 5000 mJ / cm 2 or less.
- the present invention also provides an optical device provided with the molded product.
- the present invention relates to the following.
- a molded product according to [1] wherein the thickness of the thinnest part of the molded product is 0.2 mm or less.
- the compound represented by the formula (a) is (3,4,3 ′, 4′-diepoxy) bicyclohexyl and / or bis (3,4-epoxycyclohexylmethyl) ether [4] or The molded product according to [5].
- the oxetane compound (B) is converted into 3-methoxyoxetane, 3-ethoxyoxetane, 3-propoxyoxetane, 3-isopropoxyoxetane, 3- (n-butoxy) oxetane, 3-isobutoxyoxetane, 3- (s -Butoxy) oxetane, 3- (t-butoxy) oxetane, 3-pentyloxyoxetane, 3-hexyloxyoxetane, 3-heptyloxyoxetane, 3-octyloxyoxetane, 3- (1-propenyloxy) oxetane, 3- Cyclohexyloxyoxetane, 3- (4-methylcyclohexyloxy) oxetane, 3-[(2-perfluorobutyl) ethoxy] oxetane, 3-phenoxyox
- the anion moiety is SbF 6 ⁇ , or [(Y) s B (Phf) 4 ⁇ s ] (wherein Y represents a phenyl group or a biphenylyl group. Phf represents hydrogen.
- the molded product according to any one of [14].
- the content of the cationic polymerization initiator (C) is 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the curable compound contained in the curable composition.
- the molded product according to any one of the above. [17] The molded article according to any one of [1] to [16], wherein the curable composition further contains an antioxidant (D).
- the antioxidant (D) is a phenol-based antioxidant and / or a phosphorus-based antioxidant.
- the content of the antioxidant (D) is 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the curable compound contained in the curable composition, according to [17] or [18] Moldings.
- Step 1 Step of filling a transparent array mold with a photocurable composition containing an epoxy compound
- Step 2 Step of irradiating the photocurable composition with light to obtain a molded product array
- Step 3 Molded product array
- An optical device comprising the molded product according to any one of [1] to [21].
- [27] The optical device according to [26], wherein the optical device is a portable electronic device or a vehicle-mounted electronic device.
- the molded product of the present invention is a molded product having a shape that exhibits a light condensing or light diffusing effect, and is excellent in transferability, mechanical strength, and heat resistance of a mold (mold), and has an uneven thickness ratio of 5 or more. It is. Therefore, it is possible to cope with downsizing and high functionality of the optical device including the molded product.
- the molded product of the present invention is excellent in heat resistance, it is not necessary to mount in a separate process, and it can be mounted on a substrate by reflow soldering (particularly lead-free soldering) together with other components, which is excellent.
- An optical device on which the molded product is mounted can be manufactured with work efficiency. Furthermore, it can be used for in-vehicle electronic devices that require heat resistance.
- the curable composition in the present invention contains an epoxy compound as a curable compound (in particular, a cationic curable compound).
- the epoxy compound examples include aromatic glycidyl ether type epoxy compounds (for example, bisphenol A type diglycidyl ether and bisphenol F type diglycidyl ether); alicyclic glycidyl ether type epoxy compounds (for example, hydrogenated bisphenol A type diesters). Glycidyl ether, hydrogenated bisphenol F-type diglycidyl ether, etc.); aliphatic glycidyl ether-based epoxy compounds; glycidyl ester-based epoxy compounds; glycidyl amine-based epoxy compounds; alicyclic epoxy compounds; .
- An epoxy compound can be used individually by 1 type or in combination of 2 or more types.
- an alicyclic epoxy compound is contained in that a cured product having excellent mechanical strength (for example, a flexural modulus of 2.5 GPa or more) is obtained.
- an alicyclic epoxy compound is a compound which has an alicyclic epoxy group (for example, cyclohexene oxide group etc.) comprised by two adjacent carbon atoms and oxygen atoms which comprise an alicyclic ring. .
- the compound represented by a following formula (a) can be mentioned, for example.
- R 1 to R 18 in the above formula (a) are the same or different and are a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may contain a halogen atom, or an alkoxy group which may have a substituent.
- X represents a single bond or a linking group.
- Examples of the halogen atom in R 1 to R 18 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the hydrocarbon group for R 1 to R 18 is preferably a hydrocarbon group having 1 to 20 carbon atoms.
- the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.
- an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable.
- a C 1- group such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl, dodecyl group and the like.
- alkyl groups (preferably C 1-10 alkyl groups, particularly preferably C 1-4 alkyl groups); vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1
- a C 2-20 alkenyl group (preferably a C 2-10 alkenyl group, particularly preferably a C 2-4 alkenyl group) such as a pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl group
- a C 2-20 alkynyl group such as a propynyl group (preferably a C 2-10 alkynyl group, particularly preferably a C 2-4 alkynyl group) can be exemplified.
- the alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 15 carbon atoms, for example, a C 3-12 cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclododecyl group; C 3-12 cycloalkenyl groups such as hexenyl groups; C 4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl and bicycloheptenyl groups.
- a C 3-12 cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclododecyl group
- C 3-12 cycloalkenyl groups such as hexenyl groups
- C 4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl and bicycloheptenyl groups.
- the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, and examples thereof include C 6-14 aryl groups such as phenyl and naphthyl groups (preferably C 6-10 aryl groups). be able to.
- the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in a group in which two or more groups selected from the above-described aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are bonded to each other.
- the bonded group include a C 3-12 cycloalkyl-substituted C 1-20 alkyl group such as a cyclohexylmethyl group; a C 1-20 alkyl-substituted C 3-12 cycloalkyl group such as a methylcyclohexyl group. Can do.
- Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include, for example, a C 7-18 aralkyl group such as a benzyl group or a phenethyl group (particularly a C 7-10 aralkyl group); 6-14 aryl substituted C 2-20 alkenyl group; C 1-20 alkyl substituted C 6-14 aryl group such as tolyl group; C 2-20 alkenyl substituted C 6-14 aryl group such as styryl group, etc. it can.
- a C 7-18 aralkyl group such as a benzyl group or a phenethyl group (particularly a C 7-10 aralkyl group)
- 6-14 aryl substituted C 2-20 alkenyl group C 1-20 alkyl substituted C 6-14 aryl group such as tolyl group
- C 2-20 alkenyl substituted C 6-14 aryl group such as styryl group, etc. it
- hydrocarbon group optionally containing an oxygen atom or a halogen atom in R 1 to R 18 at least one hydrogen atom in the above hydrocarbon group is substituted with a group having an oxygen atom or a group having a halogen atom.
- the group etc. can be mentioned.
- the group having an oxygen atom include hydroxyl group; hydroperoxy group; C 1-10 alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy group; C 2-10 such as allyloxy group.
- alkoxy group in R 1 to R 18 examples include C 1-10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy groups and the like.
- alkoxy group may have include, for example, a halogen atom, a hydroxyl group, a C 1-10 alkoxy group, a C 2-10 alkenyloxy group, a C 6-14 aryloxy group, a C 1-10 Acyloxy group, mercapto group, C 1-10 alkylthio group, C 2-10 alkenylthio group, C 6-14 arylthio group, C 7-18 aralkylthio group, carboxyl group, C 1-10 alkoxycarbonyl group, C 6- 14 aryloxycarbonyl group, C 7-18 aralkyloxycarbonyl group, amino group, mono or di C 1-10 alkylamino group, C 1-10 acylamino group, epoxy group-containing group, oxetanyl group-containing group, C 1-10 And an acyl group, an oxo group, and a group in which two or more of these are bonded through a single bond or a C 1-10 al
- R 1 to R 18 are preferably hydrogen atoms.
- X in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms).
- the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, an amide group, and a plurality of these. The group etc. which were connected individually can be mentioned.
- divalent hydrocarbon group examples include linear or branched C 1-18 alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups (preferably linear or branched chain).
- C 1-3 alkylene group examples include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, Examples thereof include a C 3-12 cycloalkylene group such as a cyclohexylidene group, and a C 3-12 cycloalkylidene group (preferably a C 3-6 cycloalkylene group and a C 3-6 cycloalkylidene group).
- alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like.
- the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
- Representative examples of the compound represented by the above formula (a) include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4,3 ′, 4′-diepoxy) biphenyl. Cyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxy) And cyclohexane-1-yl) propane and 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane. These can be used alone or in combination of two or more.
- the epoxy compound (A) may contain other epoxy compounds in addition to the alicyclic epoxy compound, and the glycidyl ether type epoxy compound (especially aromatic glycidyl ether) in that the refractive index can be adjusted. It is preferable to contain an epoxy-based epoxy compound and / or an alicyclic glycidyl ether-based epoxy compound).
- the content of the epoxy compound (A) in the total amount (100% by weight) of the curable composition contained in the curable composition (when two or more types are contained, the total amount) is, for example, 30 to 90% by weight, preferably 50 to 90%. % By weight, particularly preferably 60 to 85% by weight.
- content of a component (A) is less than the said range, there exists a tendency for the intensity
- content of a component (A) exceeds the said range there exists a tendency for sclerosis
- the content of the alicyclic epoxy compound in the total amount (100% by weight) of the curable composition contained in the curable composition is, for example, 30 to 80% by weight, preferably 30%. It is ⁇ 70% by weight, particularly preferably 40 to 60% by weight.
- content of an alicyclic epoxy compound is less than the said range, there exists a tendency for sclerosis
- content of the alicyclic epoxy compound exceeds the above range, the cured product tends to be brittle.
- the curable composition in the present invention may contain other curable compounds (particularly, cationic curable compounds) in addition to the epoxy compound (A), and the inclusion of an oxetane compound may improve the curability. This is preferable in that it can be further improved.
- the oxetane compound is represented, for example, by the following formula (b).
- R a represents a monovalent organic group
- R b represents a hydrogen atom or an ethyl group
- m represents an integer of 0 or more.
- the monovalent organic group in Ra includes a monovalent hydrocarbon group, a monovalent heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group). Etc.), substituted carbamoyl groups (N-alkylcarbamoyl groups, N-arylcarbamoyl groups, etc.), acyl groups (aliphatic acyl groups such as acetyl groups; aromatic acyl groups such as benzoyl groups), and two or more of these A monovalent group bonded through a single bond or a linking group is included.
- Examples of the monovalent hydrocarbon group include the same examples as R 1 to R 18 in the above formula (a).
- the monovalent hydrocarbon group includes various substituents [eg, halogen atom, oxo group, hydroxyl group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, Substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] You may have.
- the hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
- heterocyclic ring constituting the heterocyclic group a 3- to 10-membered ring having a carbon atom and at least one hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) in the atoms constituting the ring (preferably 4 to 6-membered rings), and condensed rings thereof.
- heteroatom for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.
- a heterocycle containing an oxygen atom as a hetero atom for example, a 4-membered ring such as an oxetane ring; a 5-membered ring such as a furan ring, tetrahydrofuran ring, oxazole ring, isoxazole ring, ⁇ -butyrolactone ring; 4- 6-membered ring such as oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring; condensed ring such as benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring; 3-oxatricyclo [4.3.1.1 4,8 ] undecan-2-one ring, bridged ring such as 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one ring), heteroatom
- a heterocycle containing a sulfur atom as (for example,
- the heterocyclic group includes an alkyl group (for example, a C 1-4 alkyl group such as a methyl group and an ethyl group), a cycloalkyl group (for example, C 3-12 cycloalkyl group) and an aryl group (for example, a C 6-14 aryl group such as a phenyl group or a naphthyl group) may have a substituent.
- alkyl group for example, a C 1-4 alkyl group such as a methyl group and an ethyl group
- a cycloalkyl group for example, C 3-12 cycloalkyl group
- an aryl group for example, a C 6-14 aryl group such as a phenyl group or a naphthyl group
- linking group examples include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond. (—OCOO—), silyl bond (—Si—), a group in which a plurality of these are linked, and the like.
- Examples of the compound represented by the formula (b) include 3-methoxyoxetane, 3-ethoxyoxetane, 3-propoxyoxetane, 3-isopropoxyoxetane, 3- (n-butoxy) oxetane, and 3-isobutoxyoxetane.
- oxetane compounds include “Aron oxetane OXT-101”, “Aron oxetane OXT-121”, “Aron oxetane OXT-212”, “Aron oxetane OXT-211”, “Aron oxetane OXT-213”, “Aron oxetane”.
- Commercial products such as “OXT-221” and “Aron Oxetane OXT-610” (manufactured by Toagosei Co., Ltd.) can be used.
- the content of the oxetane compound in the total amount of the curable compound (100% by weight) contained in the curable composition is, for example, 5 to 40% by weight, preferably 5 to 30% by weight, Particularly preferred is 10 to 30% by weight.
- the oxetane compound is contained in the above range, it is preferable in that the effect of improving the curability can be obtained while ensuring the strength of the cured product.
- the curable composition in the present invention may contain other curable compounds (well-known and commonly used cationic curable compounds, radical curable compounds, etc.) in addition to the epoxy compound (A) and the oxetane compound (B).
- the content of other curable compounds (the total amount when two or more are included) is, for example, 30% by weight or less, preferably 20% of the total amount (100% by weight) of the curable compound contained in the curable composition. % By weight or less, particularly preferably 10% by weight or less, most preferably 5% by weight or less. If the content of the other curable compound exceeds the above range, the effect of the present invention tends to be difficult to obtain.
- the curable composition preferably contains a cationic polymerization initiator.
- the cationic polymerization initiator includes a photocationic polymerization initiator and a thermal cationic polymerization initiator.
- the cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light and initiates a curing reaction of the cationic curable compound contained in the curable composition, and includes a cation moiety that absorbs light and a source of acid generation. It consists of A photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
- Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salts. And the like, and the like.
- a sulfonium salt compound in that a cured product having excellent curability can be formed.
- the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and 4- (4-biphenylylthio) phenyl.
- arylsulfonium ions such as -4-biphenylylphenylsulfonium ion and tri-p-tolylsulfonium ion (particularly, triarylsulfonium ion).
- Y represents a phenyl group or a biphenylyl group.
- Phf represents at least one hydrogen atom
- BF 4 ⁇ [(Rf) t PF 6-t ] - (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, t: an integer of 0 to 5), AsF 6 ⁇ , SbF 6 ⁇ , SbF 5 OH ⁇ and the like.
- the cationic photopolymerization initiator whose anion portion is SbF 6 ⁇ or [(Y) s B (Phf) 4-s ] has high activity as an initiator and has high curability. It is preferable at the point which can have and can obtain the hardened
- the thermal cationic polymerization initiator is a compound that generates an acid by heat treatment and initiates a curing reaction of the cationic curable compound contained in the curable composition, and generates a cation moiety that absorbs heat and an acid. It consists of the anion part which becomes the source.
- a thermal cationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
- thermal cationic polymerization initiator of the present invention examples include iodonium salt compounds and sulfonium salt compounds.
- Examples of the cationic part of the thermal cationic polymerization initiator include 4-hydroxyphenyl-methyl-benzylsulfonium ion, 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium ion, 4-hydroxyphenyl-methyl-1-naphthyl.
- Examples thereof include monoarylsulfonium ions such as methylsulfonium ion and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium ion.
- Examples of the anion portion of the thermal cationic polymerization initiator include the same examples as the anion portion of the photocationic polymerization initiator.
- thermal cationic polymerization initiator examples include 4-hydroxyphenyl-methyl-benzylsulfonium phenyltris (pentafluorophenyl) borate, 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium phenyltris (pentafluorophenyl) borate 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, phenyltris (pentafluorophenyl) borate, p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium, phenyltris (pentafluorophenyl) borate, and the like.
- the content of the cationic polymerization initiator is, for example, 0.1 to 10 with respect to 100 parts by weight of the curable compound contained in the curable composition (particularly, the cationic curable compound, the total amount when two or more are included). 0.0 parts by weight, preferably 0.1 to 5.0 parts by weight, particularly preferably 0.2 to 3.0 parts by weight, most preferably 0.2 parts by weight or more and less than 1.0 parts by weight.
- content of a cationic polymerization initiator is less than the said range, there exists a tendency for sclerosis
- the content of the cationic polymerization initiator exceeds the above range, the cured product tends to be easily colored.
- the curable composition preferably contains a cationic photopolymerization initiator, that is, the curable composition is preferably a photocurable composition in terms of excellent storage stability.
- the curable composition in the present invention contains other components in addition to the epoxy compound (A), oxetane compound (B), and cationic polymerization initiator (C) as long as the effects of the present invention are not impaired. Also good.
- other components include an antioxidant, a photosensitizer, an antifoaming agent, a leveling agent, a coupling agent, a surfactant, a flame retardant, an ultraviolet absorber, and a colorant. These can be used alone or in combination of two or more.
- an antioxidant (D) in that the heat resistance of the resulting cured product can be further improved.
- the antioxidant examples include a phenol-based antioxidant, a phosphorus-based antioxidant, a thioester-based antioxidant, and an amine-based antioxidant.
- a phenol-based antioxidant and / or a phosphorus-based antioxidant because the heat resistance of the resulting cured product can be further improved.
- phenolic antioxidants examples include pentaerythritol tetrakis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-t-butyl).
- the product names “Irganox 1010”, “Irganox 1035”, “Irganox 1076”, “Irganox 1098”, “Irganox 1135”, “Irganox 1330”, “Irganox 1726”, “Irganox 1726”, “1425” Commercial products such as BASF may be used.
- Examples of phosphorus antioxidants include 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2 , 6-Di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2,2′-methylenebis (4,6-di-) Examples thereof include t-butylphenyl) -2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and the like.
- trade names “PEP-8”, “PEP-8W”, “PEP-36 / 36A”, “HP-10”, “2112”, “2112RG”, “1178” Commercial products such as ADEKA
- the content of the antioxidant (D) (when 2 or more types are contained, the total amount thereof) is a curable compound contained in the curable composition (particularly a cationic curable compound, when 2 or more types are contained, the total amount thereof).
- a curable compound contained in the curable composition particularly a cationic curable compound, when 2 or more types are contained, the total amount thereof.
- 0.1 to 10.0 parts by weight preferably 0.5 to 5.0 parts by weight, and particularly preferably 0.5 to 3.0 parts by weight with respect to 100 parts by weight.
- the curable composition may contain a colorant.
- the colorant or pigment includes pigments and dyes. These can be used alone or in combination of two or more.
- the pigment examples include inorganic pigments [carbon black, chromium oxide, iron oxide, titanium black, acetylene black, lamp black, bone black, graphite, iron black, copper chrome black, copper iron manganese black, cobalt iron chrome.
- Black ruthenium oxide, graphite, metal fine particles (for example, aluminum), metal oxide fine particles, composite oxide fine particles, metal sulfide fine particles, metal nitride fine particles, etc.]
- organic pigments [perylene black, cyanine black, aniline black] Azo pigments, anthraquinone pigments, isoindolinone pigments, indanthrene pigments, indigo pigments, quinacridone pigments, dioxazine pigments, tetraazaporphyrin pigments, triarylmethane pigments, phthalocyanine pigments, perylene Pigments Benzimidazolone pigments, rhodamine pigments, the surface of the inorganic pigment and a
- the content of the colorant (when two or more types are contained, the total amount) can be appropriately adjusted according to the use, and is, for example, about 10 to 300 ppm of the total amount of the curable composition, and the lower limit is preferably 50 ppm. Particularly preferred is 100 ppm.
- the curable composition can be prepared, for example, by stirring and mixing the above components at a predetermined ratio and defoaming under vacuum as necessary.
- the curable composition has a low viscosity and an excellent mold filling property.
- the viscosity [at 25 ° C., at a shear rate of 20 (1 / s)] is, for example, 0.01 to 10.00 Pa ⁇ s, preferably 0.1 to 5.0 Pa ⁇ s, particularly preferably 0.1 to 1.0 Pa ⁇ s.
- the viscosity can be measured using a rheometer (trade name “PHYSICA UDS200”, manufactured by Anton Paar).
- the said curable composition is excellent in sclerosis
- the cured product has excellent mechanical strength.
- the bending elastic modulus of a cured product having a thickness of 1 mm obtained by curing by the method of the Examples [JIS K 7171 (2008) compliant, provided that a test piece ( Measured at a distance between supporting points of 16 mm] is 2.5 GPa or more, preferably 2.6 GPa or more, and particularly preferably 2.7 GPa or more.
- the upper limit of the flexural modulus is, for example, about 3.8 GPa.
- the cured product is excellent in heat resistance and can retain its shape even when subjected to the heat test described in the examples. Therefore, the molded product of the present invention made of the cured product can be mounted on the substrate by reflow soldering.
- the molded product of the present invention can be produced by subjecting the curable composition to casting molding.
- the concave portion (5) of the lower mold (4) is filled with the curable composition (6a) and covered with the upper mold (7), and then subjected to light irradiation and / or heat treatment.
- a mold used for casting molding a mold having one concave portion having an inverted shape of a molded product, or an array mold having a plurality of the concave portions (a plurality of concave portions may be arranged at random, at equal intervals) May be arranged).
- an array mold it is particularly preferable to use an array mold in that the molded product can be mass-produced and the production efficiency can be improved.
- the molded product of the present invention is particularly preferably produced through the following steps.
- Step 1 Step of filling a transparent array mold with a photocurable composition containing an epoxy compound
- Step 2 Step of irradiating the photocurable composition with light to obtain a molded product array
- Step 3 Molded product array The process of separating
- the transparent array mold may be composed of a plurality of parts such as a lower mold and an upper mold. Further, the transparent array mold may be subjected to a release treatment (for example, application of a release agent) in advance.
- Step 2 is a step of curing the photocurable composition.
- light active energy rays
- infrared rays, visible rays, ultraviolet rays, X rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays are used. Any of these can be used.
- ultraviolet rays are preferable in terms of excellent handleability.
- UV irradiation for example, UV-LED (wavelength is 350 to 450 nm, preferably 350 to 400 nm), high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, carbon arc, metal halide lamp, sunlight, laser, etc. are used. can do. Since the photocurable composition has excellent curability, the curing reaction can be rapidly advanced even by light irradiation with a UV-LED.
- the integrated light amount it is preferable to adjust the integrated light amount to, for example, 5000 mJ / cm 2 or less (for example, 2500 to 5000 mJ / cm 2 ) when ultraviolet light is irradiated.
- the molded product array is obtained by releasing the mold. Further, post-bake treatment (for example, heating at 80 to 180 ° C. for 5 to 30 minutes) may be performed before or after release, as necessary.
- Process 3 is a process in which a molded product array, which is a structure in which a plurality of molded products are connected through a connecting part, is cut at the connecting part and separated into pieces, that is, a dicing process (see FIG. 6).
- the cutting is performed using a cutting means such as a dicing blade.
- the manufacturing method of the molded product of the present invention is a method of condensing or diffusing light such as a flash lens of a camera in a portable electronic device such as a mobile phone, a smartphone, or a tablet PC, or a lens or prism used in an in-vehicle electronic device. It is suitable as a method for producing a molded product (in particular, a Fresnel lens) having a special shape having an effect.
- the molded product of the present invention obtained by the above production method is a cured product of the above-described curable composition and is a cured product having excellent mechanical strength, and has an uneven thickness ratio (thickest part thickness / thinnest part).
- the thickness of the thinnest part is, for example, 0.2 mm or less, preferably 0.05 to 0.2 mm, particularly preferably 0.1 to 0.2 mm.
- the thickness of the thickest part is, for example, 0.5 mm or more, preferably 0.5 to 2.0 mm, particularly preferably 0.8 to 2.0 mm.
- the molded article having the light condensing or light diffusing effect of the present invention includes a flash lens of a camera in a portable electronic device such as a mobile phone, a smartphone, and a tablet PC, and a lens or prism used in an in-vehicle electronic device (particularly, Fresnel). Lenses; see FIGS. 1-3) are preferred.
- the Fresnel lens is disclosed in JP 2014-38349 A, JP 2012-128106 A, JP 2013-137442 A, JP 04-127101 A, JP 2002-264140 A, JP 2610029, As described in JP-A-9-141663, JP-A-6-11769, etc., a prism having a lens surface (1) and a non-lens surface (2) on its surface, the cross section of which is This is a lens in which a plurality of prisms each having a mountain shape are formed in a step shape.
- the angle ⁇ formed by the lens surface (1) and the reference surface (3) decreases continuously (or increases) toward the center, and when only the lens surface (1) is continuous, one angle A convex lens (or concave lens) is formed (see FIG. 4).
- the molded product of the present invention is excellent in heat resistance. Therefore, the special shape can be maintained even when subjected to a substrate mounting process in which soldering (particularly lead-free soldering) is performed using a reflow furnace. It can also be used for in-vehicle electronic devices that require heat resistance.
- the molded product of the present invention is an integrally molded product and can suppress the occurrence of weld lines, and is therefore excellent in mechanical strength and aesthetics.
- An optical device includes the above-described molded product.
- the optical device include portable electronic devices such as mobile phones, smartphones, and tablet PCs; near infrared sensors, millimeter wave radars, LED spot illumination devices, near infrared LED illumination devices, mirror monitors, meter panels, and heads.
- In-vehicle electronic devices such as a combiner for mount display (projection type) and a combiner for head-up display are included.
- the molded product has sufficient heat resistance to be mounted on a substrate by reflow soldering. Therefore, the optical device of the present invention does not need to be mounted in a separate process, and can be mounted collectively by a reflow process, and can be manufactured efficiently and at low cost.
- the obtained bicyclohexyl-3,3′-diene (243 g) and ethyl acetate (730 g) were charged into a reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was controlled to 37.5 ° C. Then, 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over about 3 hours. After completion of the dropwise addition, the reaction was terminated by aging at 40 ° C. for 1 hour.
- reaction product was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 270 g of a reaction product.
- the oxirane oxygen concentration of the reaction product was 15.0% by weight.
- Production Example 2 (Production of bis (3,4-epoxycyclohexylmethyl) ether (a-2)) Sodium hydroxide (granular form) (499 g, 12.48 mol) and toluene (727 mL) were added to a 5 L reactor, and after purging with nitrogen, a solution of tetrahydrobenzyl alcohol (420 g, 3.74 mol) in toluene (484 mL) was added. And aged at 70 ° C. for 1.5 hours.
- the viscosity (Pa ⁇ s) of the curable composition was measured using a rheometer (trade name “PHYSICA UDS200”, manufactured by Anton Paar) under conditions of a temperature of 25 ° C. and a shear rate of 20 (1 / s).
- the thickest part and the thinnest part of the obtained molded product were observed using a CCD camera (trade name “VH-Z20UR”, manufactured by Keyence Corporation), and the thickest part thickness (H) and thinnest part thickness were observed. (H) was measured and the thickness deviation ratio (H / h) was calculated. Further, the mold shape transferability was evaluated according to the following criteria. Evaluation criteria Good transferability (O): When the molded product has the same shape as the concave shape of the lower mold. Poor transferability (X): When the molded product is damaged or has a shape different from the concave shape of the lower mold.
- each component in Table 1 is as follows.
- ⁇ Curable compound> (A-1): (3,4,3 ′, 4′-diepoxy) bicyclohexyl obtained in Production Example 1 (a-2): Bis (3,4-epoxycyclohexylmethyl) obtained in Production Example 2 )
- Ether CELLOXIDE 2021P 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, manufactured by Daicel Corporation
- YL983U Bisphenol F type diglycidyl ether, trade name “YL983U”, Mitsubishi YX8000 manufactured by Chemical Co., Ltd .: hydrogenated bisphenol A type diglycidyl ether, trade name “YX8000”, manufactured by Mitsubishi Chemical Co., Ltd.
- OXT221 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ Oxetane, trade name "Aron Oxetane OXT-221", Toagoi IRR214K: Diacrylate having a dicyclopentadiene skeleton, trade name “IRR214K”, manufactured by Daicel Ornex Co., Ltd.
- PETIA Pentaerythritol (tri / tetra) acrylate, trade name “PETIA”, Daicel Ornex ( IBOA manufactured by: Co., Ltd .: Isobornyl acrylate, trade name “IBOA-B”, manufactured by Daicel Ornex Co., Ltd.
- CPI-101A Photocationic polymerization initiator, propylene carbonate 50% solution of 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, trade name “CPI-101A”, San Apro Co., Ltd.
- CPI-100P Photocationic polymerization initiation Agent, 50% propylene carbonate solution of 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, trade name “CPI-100P”, manufactured by San Apro Co., Ltd.
- Irgacure 184 Photocationic polymerization initiator, 4- (phenylthio) phenyldiphenyl Sulfonium phenyltris (pentafluorophenyl) borate
- Irgacure 184 photoradical polymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone, trade name “Irgacure 184”, BAS Company made ⁇ antioxidants>
- Irganox 1010 Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], trade name “Irganox 1010”, manufactured by BASF, HP-10: 2,2′-methylenebis (4,6 -Di-t-butylphenyl) -2-ethylhexyl phosphite, trade name “HP-10”, manufactured by ADEKA Corporation
- the molded product of the present invention is a molded product having a shape that exhibits a light condensing or light diffusing effect, and is excellent in transferability, mechanical strength, and heat resistance of a mold (mold), and has an uneven thickness ratio of 5 or more. It is. Therefore, it is possible to cope with downsizing and high functionality of the optical device including the molded product.
- the molded product of the present invention is excellent in heat resistance, it is not necessary to mount in a separate process, and it can be mounted on a substrate by reflow soldering (particularly lead-free soldering) together with other components, which is excellent.
- An optical device on which the molded product is mounted can be manufactured with work efficiency. Furthermore, it can be used for in-vehicle electronic devices that require heat resistance.
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Abstract
Description
本発明の他の目的は、集光又は光拡散効果を発揮する形状を有する成形物であって、機械強度と耐熱性に優れ、高偏肉比と薄肉部を有する成形物を提供することにある。
本発明の他の目的は、集光又は光拡散効果を発揮する形状を有する成形物であって、金型(モールド)の転写性、機械強度、及び耐熱性に優れ、高偏肉比と薄肉部を有する成形物を提供することにある。
本発明の他の目的は、前記成形物の製造方法を提供することにある。
本発明の他の目的は、前記成形物を備えた光学装置を提供することにある。
工程1:エポキシ化合物(A)を含有する光硬化性組成物を透明アレイモールドに充填する工程
工程2:光硬化性組成物に光照射を行い、成形物アレイを得る工程
工程3:成形物アレイを個片化する工程
[1] エポキシ化合物(A)を含有する硬化性組成物の硬化物であって、曲げ弾性率[JIS K 7171(2008年)準拠、但し、試験片(長さ20mm×幅2.5mm×厚み0.5mm)を使用し、支点間距離16mmで測定]が2.5GPa以上の硬化物から成る、偏肉比(最厚部厚み/最薄部厚み)が5以上の、集光又は光拡散効果を有する成形物。
[2] 成形物の最薄部厚みが0.2mm以下である[1]に記載の成形物。
[3] 成形物の最厚部厚みが0.5mm以上である[1]又は[2]に記載の成形物。
[4] エポキシ化合物(A)が、式(a)で表される化合物を含有する[1]~[3]の何れか1つに記載の成形物。
[5] エポキシ化合物(A)が、式(a)で表される化合物であって、エステル結合を含まない化合物を含有する[4]に記載の成形物。
[6] 式(a)で表される化合物が、(3,4,3’,4’-ジエポキシ)ビシクロへキシル、ビス(3,4-エポキシシクロヘキシルメチル)エーテル、及び3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレートから選択される少なくとも1種の化合物である[4]に記載の成形物。
[7] 式(a)で表される化合物が、(3,4,3’,4’-ジエポキシ)ビシクロへキシル及び/又はビス(3,4-エポキシシクロヘキシルメチル)エーテルである[4]又は[5]に記載の成形物。
[8] エポキシ化合物(A)が、式(a)で表される化合物とグリシジルエーテル系エポキシ化合物を含有する[4]~[7]の何れか1つに記載の成形物。
[9] エポキシ化合物(A)の含有量が、硬化性組成物に含まれる硬化性化合物全量の30~90重量%である[1]~[8]の何れか1つに記載の成形物。
[10] 硬化性組成物が、エポキシ化合物(A)、オキセタン化合物(B)、及びカチオン重合開始剤(C)を含有する[1]~[9]の何れか1つに記載の成形物。
[11] オキセタン化合物(B)が、3-メトキシオキセタン、3-エトキシオキセタン、3-プロポキシオキセタン、3-イソプロポキシオキセタン、3-(n-ブトキシ)オキセタン、3-イソブトキシオキセタン、3-(s-ブトキシ)オキセタン、3-(t-ブトキシ)オキセタン、3-ペンチルオキシオキセタン、3-ヘキシルオキシオキセタン、3-ヘプチルオキシオキセタン、3-オクチルオキシオキセタン、3-(1-プロペニルオキシ)オキセタン、3-シクロヘキシルオキシオキセタン、3-(4-メチルシクロヘキシルオキシ)オキセタン、3-[(2-パーフルオロブチル)エトキシ]オキセタン、3-フェノキシオキセタン、3-(4-メチルフェノキシ)オキセタン、3-(3-クロロ-1-プロポキシ)オキセタン、3-(3-ブロモ-1-プロポキシ)オキセタン、3-(4-フルオロフェノキシ)オキセタン、及び式(b-1)~(b-15)で表される化合物から選択される少なくとも1種の化合物である[10]に記載の成形物。
[12] オキセタン化合物(B)の含有量が、硬化性組成物に含まれる硬化性化合物全量の5~40重量%である[10]又は[11]に記載の成形物。
[13] カチオン重合開始剤(C)が光カチオン重合開始剤である[10]~[12]の何れか1つに記載の成形物。
[14] カチオン重合開始剤(C)が、スルホニウム塩系化合物である[10]~[13]の何れか1つに記載の成形物。
[15] カチオン重合開始剤(C)が、アニオン部がSbF6 -、又は[(Y)sB(Phf)4-s](式中、Yはフェニル基又はビフェニリル基を示す。Phfは水素原子の少なくとも1つが、パーフルオロアルキル基、パーフルオロアルコキシ基、及びハロゲン原子から選択される少なくとも1種で置換されたフェニル基を示す。sは0~3の整数である)である化合物である[10]~[14]の何れか1つに記載の成形物。
[16] カチオン重合開始剤(C)の含有量が、硬化性組成物に含まれる硬化性化合物100重量部に対して0.1~10.0重量部である[10]~[15]の何れか1つに記載の成形物。
[17] 硬化性組成物が、更に酸化防止剤(D)を含有する[1]~[16]の何れか1つに記載の成形物。
[18] 酸化防止剤(D)が、フェノール系酸化防止剤及び/又はリン系酸化防止剤である[17]に記載の成形物。
[19] 酸化防止剤(D)の含有量が、硬化性組成物に含まれる硬化性化合物100重量部に対して0.1~10.0重量部である[17]又は[18]に記載の成形物。
[20] 集光又は光拡散効果を有する成形物がレンズ又はプリズムである[1]~[19]の何れか1つに記載の成形物。
[21] 集光又は光拡散効果を有する成形物がフレネルレンズである[1]~[19]の何れか1つに記載の成形物。
[22] エポキシ化合物(A)を含有する硬化性組成物をキャスティング成形に付して[1]~[21]の何れか1つに記載の成形物を得る成形物の製造方法。
[23] 下記工程を有する[22]に記載の成形物の製造方法。
工程1:エポキシ化合物(A)を含有する光硬化性組成物を透明アレイモールドに充填する工程
工程2:光硬化性組成物に光照射を行い、成形物アレイを得る工程
工程3:成形物アレイを個片化する工程
[24] UV-LED(波長:350~450nm)を使用して光照射を行う[23]に記載の成形物の製造方法。
[25] 光照射の積算光量が5000mJ/cm2以下である[23]又は[24]に記載の成形物の製造方法。
[26] [1]~[21]の何れか1つに記載の成形物を備えた光学装置。
[27] 光学装置が、携帯型電子機器又は車載用電子機器である[26]に記載の光学装置。
(エポキシ化合物(A))
本発明における硬化性組成物は、硬化性化合物(特に、カチオン硬化性化合物)としてエポキシ化合物を含有する。
本発明における硬化性組成物には、上記エポキシ化合物(A)以外にも他の硬化性化合物(特に、カチオン硬化性化合物)を含有していても良く、オキセタン化合物を含有することが硬化性を一層向上することができる点で好ましい。
本発明における硬化性組成物は、上記エポキシ化合物(A)、オキセタン化合物(B)以外にも他の硬化性化合物(周知慣用のカチオン硬化性化合物、ラジカル硬化性化合物等)を含有していてもよいが、他の硬化性化合物の含有量(2種以上含有する場合はその総量)は硬化性組成物に含まれる硬化性化合物全量(100重量%)の、例えば30重量%以下、好ましくは20重量%以下、特に好ましくは10重量%以下、最も好ましくは5重量%以下である。他の硬化性化合物の含有量が上記範囲を上回ると、本発明の効果が得られにくくなる傾向がある。
前記硬化性組成物はカチオン重合開始剤を含有することが好ましい。カチオン重合開始剤には光カチオン重合開始剤と熱カチオン重合開始剤が含まれる。
本発明における硬化性組成物は、上記エポキシ化合物(A)、オキセタン化合物(B)、カチオン重合開始剤(C)以外にも、本発明の効果を損なわない範囲で他の成分を含有していてもよい。他の成分としては、例えば、酸化防止剤、光増感剤、消泡剤、レベリング剤、カップリング剤、界面活性剤、難燃剤、紫外線吸収剤、着色剤等を挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。
本発明の成形物は、上記硬化性組成物をキャスティング成形に付すことにより製造することができる。
工程1:エポキシ化合物(A)を含有する光硬化性組成物を透明アレイモールドに充填する工程
工程2:光硬化性組成物に光照射を行い、成形物アレイを得る工程
工程3:成形物アレイを個片化する工程
上記製造方法により得られる本発明の成形物は、上記硬化性組成物の硬化物であって機械強度に優れた硬化物からなる成形物であり、偏肉比(最厚部厚み/最薄部厚み)が5以上(好ましくは5~15、特に好ましくは7~12)の、集光又は光拡散効果を発揮する形状を有する成形物である。
本発明の光学装置は、上記成形物を備えることを特徴とする。前記光学装置には、例えば、携帯電話、スマートフォン、タブレットPC等の携帯型電子機器;近赤外センサ、ミリ波レーダー、LEDスポット照明装置、近赤外LED照明装置、ミラーモニター、メーターパネル、ヘッドマウントディスプレイ(投影型)用コンバイナ、ヘッドアップディスプレイ用コンバイナ等の車載用電子機器等が含まれる。前記成形物はリフロー半田付けにより基板実装するのに十分な耐熱性を有する。そのため、本発明の光学装置は、前記成形物を別工程で実装する必要がなく、リフロー処理により一括して実装が可能であり、効率よく、且つ低コストで製造することができる。
95重量%硫酸70g(0.68モル)と1,8-ジアザビシクロ[5.4.0]ウンデセン-7(DBU)55g(0.36モル)を撹拌混合して脱水触媒を調製した。
撹拌機、温度計、および脱水剤が充填され且つ保温された留出配管を具備した3Lのフラスコに、水添ビフェノール(4,4’-ジヒドロキシビシクロヘキシル)1000g(5.05モル)、上記で調製した脱水触媒125g(硫酸として0.68モル)、プソイドクメン1500gを入れ、フラスコを加熱した。内温が115℃を超えたあたりから水の生成が確認された。さらに昇温を続けてプソイドクメンの沸点まで温度を上げ(内温162~170℃)、常圧で脱水反応を行った。副生した水は留出させ、脱水管により系外に排出した。尚、脱水触媒は反応条件下において液体であり反応液中に微分散していた。3時間経過後、ほぼ理論量の水(180g)が留出したため反応終了とした。反応終了時の液を10段のオールダーショウ型の蒸留塔を用い、プソイドクメンを留去した後、内部圧力10Torr(1.33kPa)、内温137~140℃にて蒸留し、731gのビシクロヘキシル-3,3’-ジエンを得た。
また1H-NMRの測定では、δ4.5~5ppm付近の内部二重結合に由来するピークが消失し、δ3.1ppm付近にエポキシ基に由来するプロトンのピークの生成が確認された。そのため、反応生成物は、(3,4,3’,4’-ジエポキシ)ビシクロヘキシルであることが確認された。
5L反応器に水酸化ナトリウム(顆粒状)(499g、12.48モル)、及びトルエン(727mL)を加え、窒素置換した後に、テトラヒドロベンジルアルコール(420g、3.74モル)のトルエン(484mL)溶液を添加し、70℃で1.5時間熟成した。次いで、メタンスルホン酸テトラヒドロベンジル(419g、2.20モル)を添加し、3時間還流下で熟成させた後、室温まで冷却し、水(1248g)を加えて反応を停止し、分液した。分液した有機層を濃縮後、減圧蒸留を行うことにより、ジテトラヒドロベンジルエーテルを無色透明液体として得た(収率:85%)。得られたジテトラヒドロベンジルエーテルの1H-NMRスペクトルを測定した。
1H-NMR(CDCl3):δ1.23-1.33(m、2H)、1.68-1.94(m、6H)、2.02-2.15(m、6H)、3.26-3.34(m、4H)、5.63-7.70(m、4H)
下記表1に記載の各成分を配合組成(単位;重量部)に従って配合し、室温で自転公転型ミキサーを撹拌・混合することにより、均一で透明な硬化性組成物を得た。
得られた硬化性組成物、及びそれを硬化して得られた硬化物について下記評価を行った。
硬化性組成物の粘度(Pa・s)は、レオメーター(商品名「PHYSICA UDS200」、Anton Paar社製)を用い、温度25℃、せん断速度20(1/s)の条件下で測定した。
縦30mm×横20mm×厚み0.5mmのテフロン(登録商標)製のスペーサーを作製し、離型処理[商品名「オプツールHD1000」(ダイキン(株)製)に浸漬した後、24時間ドラフト内で放置]を施したスライドガラス(商品名「S2111」、松浪硝子(株)製)で挟み込みを行った。
実施例及び比較例で得られた硬化性組成物を注型し、UV-LED(商品名「ZUV-C20H」、オムロン(株)製)を使用して光照射(波長:365nm、照射強度:50~100mW/cm2、積算光量:2500~5000mJ/cm2)して硬化物を得た。
得られた硬化物を長さ20mm×幅2.5mm×厚み0.5mmのサイズに加工して得られた試験片について、引張・圧縮試験機(商品名「RTF1350」、(株)エイ・アンド・デイ製)を使用して、支点間距離を16mmに固定して測定した以外は、JIS K7171(2008年)に準拠して曲げ弾性率を測定した。
透明な下型の凹部に、実施例及び比較例で得られた硬化性組成物を充填し、透明な上型で蓋をして、UV-LED(商品名「ZUV-C20H」、オムロン(株)製)を使用して硬化性組成物に光照射(波長:365nm、照射強度:50~100mW/cm2、積算光量:2500~5000mJ/cm2)を行い、その後離型して成形物を得た(図5参照)。
得られた成形物の最厚部及び最薄部を、CCDカメラ(商品名「VH-Z20UR」、キーエンス(株)製)を使って観察し、最厚部厚み(H)、最薄部厚み(h)を測定し、偏肉比(H/h)を算出した。また、以下の基準に従ってモールド形状の転写性を評価を行った。
評価基準
転写性良好(○):成形物が下型の凹部形状と同一の形状である場合
転写性不良(×):成形物が破損、又は下型の凹部形状と異なる形状である場合
[偏肉比、及びモールド形状の転写性評価]と同様の方法で得られた成形物を、卓上リフロー炉(シンアペック社製)を使用して、JEDEC規格記載のリフロー温度プロファイル(最高温度:270℃)に基づく耐熱性試験に付した(連続3回)。
耐熱性試験後の成形物について、上記[偏肉比、及びモールド形状の転写性評価]と同様の方法で最厚部厚み(H’)、最薄部厚み(h’)を測定し、偏肉比(H’/h’)、及びモールド形状の転写性を評価を行った。
<硬化性化合物>
(a-1):製造例1で得られた(3,4,3’,4’-ジエポキシ)ビシクロヘキシル
(a-2):製造例2で得られたビス(3,4-エポキシシクロヘキシルメチル)エーテル
CELLOXIDE2021P:3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、商品名「セロキサイド2021P」、(株)ダイセル製
YL983U:ビスフェノールF型ジグリシジルエーテル、商品名「YL983U」、三菱化学(株)製
YX8000:水添ビスフェノールA型ジグリシジルエーテル、商品名「YX8000」、三菱化学(株)製
OXT221:3-エチル-3{[(3-エチルオキセタン-3-イル)メトキシ]メチル}オキセタン、商品名「アロンオキセタンOXT-221」、東亞合成(株)製
IRR214K:ジシクロペンタジエン骨格を有するジアクリレート、商品名「IRR214K」、ダイセル・オルネクス(株)製
PETIA:ペンタエリスリトール(トリ/テトラ)アクリレート、商品名「PETIA」、ダイセル・オルネクス(株)製
IBOA:イソボルニルアクリレート、商品名「IBOA-B」、ダイセル・オルネクス(株)製
<重合開始剤>
CPI-101A:光カチオン重合開始剤、4-(フェニルチオ)フェニルジフェニルスルホニウム ヘキサフルオロアンチモネートのプロピレンカーボネート50%溶液、商品名「CPI-101A」、サンアプロ(株)製
CPI-100P:光カチオン重合開始剤、4-(フェニルチオ)フェニルジフェニルスルホニウム ヘキサフルオロホスフェートのプロピレンカーボネート50%溶液、商品名「CPI-100P」、サンアプロ(株)製
c-1:光カチオン重合開始剤、4-(フェニルチオ)フェニルジフェニルスルホニウム フェニルトリス(ペンタフルオロフェニル)ボレート
Irgacure184:光ラジカル重合開始剤、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、商品名「Irgacure184」、BASF社製
<酸化防止剤>
Irganox1010:ペンタエリスリトール テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェノール)プロピオネート]、商品名「Irganox1010」、BASF社製
HP-10:2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)-2-エチルヘキシルホスファイト、商品名「HP-10」、(株)ADEKA製
2 非レンズ面
3 基準面
4 下型
5 下型凹部
6a 硬化性組成物
6b 成形物(=硬化性組成物の硬化物)
7 上型
8 切断ライン
9 成形物アレイ
10 個片化して得られた成形物
Claims (13)
- エポキシ化合物(A)を含有する硬化性組成物の硬化物であって、曲げ弾性率[JIS K 7171(2008年)準拠、但し、試験片(長さ20mm×幅2.5mm×厚み0.5mm)を使用し、支点間距離16mmで測定]が2.5GPa以上の硬化物から成る、偏肉比(最厚部厚み/最薄部厚み)が5以上の、集光又は光拡散効果を有する成形物。
- 成形物の最薄部厚みが0.2mm以下である請求項1に記載の成形物。
- エポキシ化合物(A)が、式(a)で表される化合物であって、エステル結合を含まない化合物を含有する請求項3に記載の成形物。
- 硬化性組成物が、エポキシ化合物(A)、オキセタン化合物(B)、及びカチオン重合開始剤(C)を含有する請求項1~4の何れか1項に記載の成形物。
- カチオン重合開始剤(C)が光カチオン重合開始剤である請求項5に記載の成形物。
- 硬化性組成物が、更に酸化防止剤(D)を含有する請求項5又は6に記載の成形物。
- 集光又は光拡散効果を有する成形物がフレネルレンズである請求項1~7の何れか1項に記載の成形物。
- エポキシ化合物(A)を含有する硬化性組成物をキャスティング成形に付して請求項1~8の何れか1項に記載の成形物を得る成形物の製造方法。
- 下記工程を有する請求項9に記載の成形物の製造方法。
工程1:エポキシ化合物(A)を含有する光硬化性組成物を透明アレイモールドに充填する工程
工程2:光硬化性組成物に光照射を行い、成形物アレイを得る工程
工程3:成形物アレイを個片化する工程 - UV-LED(波長:350~450nm)を使用して光照射を行う請求項10に記載の成形物の製造方法。
- 光照射の積算光量が5000mJ/cm2以下である請求項10又は11に記載の成形物の製造方法。
- 請求項1~8の何れか1項に記載の成形物を備えた光学装置。
Priority Applications (6)
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CN202111652603.6A CN114479010A (zh) | 2014-08-08 | 2015-08-04 | 具有特殊形状的环氧树脂成型物、以及具备该成型物的光学装置 |
KR1020177004148A KR20170039680A (ko) | 2014-08-08 | 2015-08-04 | 특수 형상을 갖는 에폭시 수지 성형물 및 그것을 구비한 광학 장치 |
CN201580039718.4A CN106662679A (zh) | 2014-08-08 | 2015-08-04 | 具有特殊形状的环氧树脂成型物、以及具备该成型物的光学装置 |
EP15829560.0A EP3196679A4 (en) | 2014-08-08 | 2015-08-04 | Specially-shaped epoxy resin molded article, and optical device provided with same |
JP2016540237A JP6474814B2 (ja) | 2014-08-08 | 2015-08-04 | 特殊形状を有するエポキシ樹脂成形物、及びそれを備えた光学装置 |
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JP2018203807A (ja) * | 2017-05-30 | 2018-12-27 | 株式会社Adeka | 重合開始剤及び該重合開始剤を含有する硬化性組成物 |
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US10351663B2 (en) | 2014-09-17 | 2019-07-16 | Daicel Corporation | Curable composition and optical element obtained using same |
JP6204420B2 (ja) * | 2015-08-07 | 2017-09-27 | 株式会社ダイセル | 硬化性組成物、及びそれを用いた光学素子 |
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Also Published As
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TW201945421A (zh) | 2019-12-01 |
US20170232695A1 (en) | 2017-08-17 |
JP6474814B2 (ja) | 2019-02-27 |
TW201612210A (en) | 2016-04-01 |
TWI662057B (zh) | 2019-06-11 |
CN106662679A (zh) | 2017-05-10 |
TW202035501A (zh) | 2020-10-01 |
US10843423B2 (en) | 2020-11-24 |
CN114479010A (zh) | 2022-05-13 |
JP2019014909A (ja) | 2019-01-31 |
EP3196679A4 (en) | 2018-03-28 |
KR20170039680A (ko) | 2017-04-11 |
EP3196679A1 (en) | 2017-07-26 |
JPWO2016021577A1 (ja) | 2017-05-25 |
TWI699382B (zh) | 2020-07-21 |
JP6652616B2 (ja) | 2020-02-26 |
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